Polymers of unsaturated compounds and processes of producing same



Patented Oct. 22, 1946 POLYMERS F UNSATUBATED COMPOUNDS AND PROCESSES OFPRODUCING SAME Edward L. Kropa, Old Greenwich, Conn., assignor toAmerican Cyanamid Company, New York, N. Y., a corporation of Maine NoDrawing. Application July 17. 1943, Serial No. 195,213

11 Claims. 1

This invention relates to resinous compositions and processes ofproducing such compositions by polymerizing or reacting a reactive resinof the alkyd type with reactive organic substances, generally solvents.to form substantially infusible, substantially insoluble resins.

One of the objects of this invention is to prepare improved resins andespecially to obtain clear and colorless gels.

It is also an object of this invention to provide potentiallypolymerizable solutions which would be stable during storage.

Still another object of this invention is to control the rate ofpolymerization of the reactive mixture, 9. well as to improve theproperties and characteristics of resulting gels.

Another object of this invention is to prepare compounds particularlysuitable for use as coating compositions and as components in coatingcompositions.

A further object of the present invention is to prepare moldingcompositions and especially to prepare clear and colorless moldedmaterials. Another object of this invention is to prepare laminatedmoldings having high strength and other desirable properties.

A still further object of this invention is to provide moldingcompositions suitable for injection molding. Other objects will beapparent from the description.

Substantially insoluble, substantially infusible resins may be preparedby means of thechemical reaction or polymerization of a mixturecontaining a resin possessing a plurality of polymerizably reactivealpha. beta enal groups and an organic substance which contains thepolymerizably reactive group CH2=CH-CH-.--. The high boiling allylcompounds are the preferred reactive organic substances. Such mixturesmay be utilized in coating compositions, in molding compositions, inlaminating, in adhesives, in casting compositions, etc.

For the sake of brevity the organic substances which contain thepolymerizably reactive group, CH==C will be referred to herein as"reactive materials" or as reactive materials containing the CH2=C groupand they are thus to be distinguished from the resins which possess apinrality of polymerizably reactive alpha, beta enal groups which aredesignated herein as "reactive resins" or as unsaturated alkyd resins.

Many oi the reactive materials containing the CH2=C group are solventsand therefore the reactive resins may be dissolved therein to iormliquid compositions which may be used as such without the addition ofany other solvent unless particularly desirable. It is to be understood,however, that I am not restricted to liquid substances which actuallyact as solvents since in some cases the organic liquid substances may infact act as a solute rather than as a solvent, it being dissolved by theresin, or a colloidal solution may be produced instead of a truesolution. Furthermore, the reactive material may be a resin containing aplurality of crn=c groups or CH2=CH-CHagroups. Such a substance could becured by a reactive resin or by a reactive substance which containspolymerizably reactive alpha, beta enal groups. Such substances may bederived from alpha, beta unsaturated organic acids, for example, byesteriflcation of such acids.

Among the reactive resins used in the practice of this invention forinteraction with the reactive material containing the CH==C group arethose which are derived from alpha, beta unsaturated organic acids and,therefore, contain the reactive groupings present in these acids.

The term acids as used herein is intended to include the anhydrides aswell as the acids themselves since the former may be used instead 01'the acid. The term alpha, beta-unsaturated organic acid as used in theart does not include acids wherein the unsaturated group is part of anaromatic-acting radical, as for example, phthalic acid, and the samedefinition is adopted herein.

The resins are preferably produced by the esteriflcation of an alpha,beta-unsaturated polycarboxylic acid with a polyhydric alcohol andparticularly a glycol. Although esterification of the acid with apolyhydric alcohol is perhaps one of the simplest, most convenient waysof obtaining a reactive resin, I am not precluded from using resinsotherwise derived from alpha, betaunsaturated organic acids. Reactiveresins suitable for my invention are any of those containing a pluralityof polymerizably reactive alpha, beta enal groups.

Panrsaarron or run POLYMERIZABLE MIX-rim:

A reactive resin such as those prepared by the esteriflcation of alpha,beta-unsaturated organic acids and a glycol or other polyhydric alcoholas illustrated above is mixed with the reactive material containing thegroup CH==C Upon adding a polymerization catalyst and subjecting themixture to polymerization conditions such as, ior example, heat, lightor a combination of both,

a substantially insoluble, substantially infuslble resin is obtained.

All of the reactive substances suitable for use according to myinvention for reaction with a reactive resin are characterized by thepresence of the reactive group CH2=C and none of them contain conjugatedcarbon-to-carbon double bonds. Compounds containing a conjugated systemof carbon-to-carbon double bonds are known to react with themselves orwith other unsaturated compounds such as the maleic esters, by a 1,2 1,4addition mechanism such as that which has become generally known as theDiels-Alder reaction. On the other hand, compounds such as those usedaccording to the present invention and which contain no conjugatedcarbon-tocarbon double bonds obviously cannot undergo this type ofreaction with the maleic esters. Accordingly, my invention is notdirected to the use of unsaturated compounds containing conjugatedsystems of carbon-to-carbon double bonds. Many substances which containa carbon-to-carbon double bond conjugated with respect to oxygen aresuitable for use according to my invention since they do not react withunsaturated a1- kyd resins in an undesirable manner, but, instead,copolymerize or interpolymerize to form substantially infusible,substantially insoluble resins.

The reactive allyl compounds which may be used are any of thosecompounds which contain the CH:=CHCH2- group and which do not have aboiling point below about 60 C. Of the allyl compounds which may be usedthe allyl esters form a large class all of which are suitable. Thereactive allyl compounds which have been found to be most suitable arethose having a high boiling point such as the diallyl esters, e. g.,diallyl maleate, diallyl fumarate, diallyl phthalate and diallylsuccinate. Other allyl compounds may also be used which are notnecessarily high boiling. As pointed out in my copending application,Serial No. 487,034, filed May 14, 1943, substantially insoluble andsubstantially infusible resins may be prepared by reacting orpolymerizing any of the following with a polymerizably reactive resin ofthe type described herein, i. e., unsaturated alkyd resins containing aplurality of alpha, beta enal groups: ailyl alcohol, methallyl alcohol,allyl acetate, allyl lactate, the allyl ester of alpha-hydroxyisobutyricacid, allyl acrylate, allyl methacrylate, diallyl carbonate, diallylmalonate, diallyl oxalate, diallyl succinate, diallyl gluconate, diallylmethylgluconate, diallyl adipate, the diallyl ester of azelaic acid,diallyl sebacate, diallyl tartronate, diallyl tartrate, diallylsilicone, diallyl silicate, diallyl fumarate, diallyl maleate, diallylmesaconate, diallyl citraconate, diallyl glutaconate, the diallyl esterof muconic acid, diallyl itaconate, diallyl phthalate, the diallyl esterof endomethylene tetrahydrophthalic anhydride, triallyl tricarballylate,trlallyl aconitate, triallyl citrate, triallyl phosphate, trimethallylphosphate, triallyl silicone, the diallyl ester of ethylene glycoldicarbonate, i. e.,

CH1=CHCH|0-t l the diallyl ester of ethylene glycol dimalonate, thediallyl ester of ethylene glycol dioxalate, the diallyl ester ofdiethylene glycol dicarbonate, the diallyl ester of diethylene glycoldimalonate, the diallyl ester of diethylene glycol dioxalate, the

CHz=CH-CH:OOC CHFCH-CHr-OCC =CHCH= cm=cHcHl-oo0 00OH1OH=OH: Anothercompound which may be employed is the tetraallyl ester obtained by thereaction of allyl malonate with chloroform in the presence of sodiumallylate and which has the following formula:

c112=cnomooc COOCHrCH=CHs Still another compound which may be employedis the compound having the following formula:

and it may be prepared by reacting allyl acetylene dicarboxylate withallyl malonate.

The polymerization catalysts include the organic superoxides, aldehydicand acidic peroxides. Among the preferred catalysts there are: theacidic peroxides, e. g., benzoyl peroxide, phthallc peroxide, succinicperoxide and benzoyl acetic peroxide; fatty oil acid peroxides, e. g.,coconut oil acid peroxides, lauric peroxide, stearic peroxide and oleicperoxide; alcohol peroxides, e. g., tertiary butyl hydroperoxide usuallycalled tertiary butyl peroxide and terpene oxides, e. g., ascaridole.Still other polymerization catalysts might be used in some instancessuch as soluble cobalt salts (particularly the linoleate andnaphthenate) p-toluene sulfonic acid, aluminum chloride, stannicchloride and boron trifluoride.

The term polymerization catalyst as used in this specification is notintended to cover oxygen contained in the resin as an impurity. Whilethis small amount of oxygen would only catalyze the reaction to a verysmall extent, in order to eliminate any ambiguity the termpolymerization catalyst is specifically defined as excluding any oxygenpresent as an impurity in the resin itself.

The concentration of catalyst employed is usually small, i. e., for thepreferred catalysts, from about 1 part catalyst per thousand parts ofthe reactive mixture to about 2 parts per hundred parts of the reactivemixture. If an inhibitor be present, up to 5% or even more of cata ystmay be necessary according to the concentration of inhibitor. Wherefillers are used which contain high concentrations of substances whichact as inhibitors, e. g., wood flour, the concentration of catalystnecessary to effect polymerization may be well above 5%.

The polymerization conditions referred to are heat, light, or acombination or both. Ultraviolet light is more eiiective than ordinarylight. The temperature of conversion depends somewhat on the boilingpoint of the reactive material and also on the pressures used. Atatmospheric pressure, as in coating and casting operations, temperaturesnear or above the boiling point are unsuitable in most instances sincesubstantial amounts of the reactive material would be lost byevaporation before the reaction between the resin and reactive materialcan be completed. Accordingly a temperature between room temperature(about 20-25 C.) and the boiling point is usually employed wherepolymerization of this nature is carried out. The rate of polymerizationdoubles for about each ten degrees (6.) rise in temperature for thisreaction. A temperature is selected which will give a suitable reactionrate and yet not cause substantial volatilization. The following tableshows the approximate polymerization temperatures most suitable for thenamed reactive materials:

Reactive material Temperature range mmtm C. Diallyl maleote Boom temp.toabout 110 0. 50 to 90 Diallylphthaiaia Roomtemp.toabouti50C. romeoObviously it will be necessary to use lower temperatures ii large orvery thick pieces are being cast because of the exothermic reaction andpoor heat conductivity of the reacting mixture.

Where suitable precautions are taken to prevent evaporation of ourreactive material or where pressure molding is used higher temperaturesthan those mentioned above could be used. Since the time of curing isdesirably much shorter (in pressure molding at elevated temperatures)and since the reactive material containing the CH2==C group would not belost so easily, a higher temperature is preferred.

The particular reactive resin, reactive material and catalyst isselected according to the type of product desired, taking into accountthe solubilities of the reactants as well as the character of theresulting gels. Some combinations of reactive resins and reactivematerials result in opaque gels while others give clear products in thegel state Obviously for many purposes the opaque gel may be used equallyas well as the clear gel. The following examples (the proportions beinggiven in parts by weight) illustrate these principles and indicateoptimum control conditions, particularly in comparison with lesssuitable control conditions:

Example 1 Diethylene glycol maleate resin and diallyl maleate were mixedin various concentrations and treated with 0.4% of benzoyl peroxide. Thefollowing results were obtained after curing four days at 58 C.

Similar results are obtained substituting diallyl tumarate and diallylphthalate.

Example 2 Ethylene glycol maleate resin (acid number and diallylphthalate were mixed in various concentrations and treated with 0.4%benzoyl peroxide. The mlxtures were heated at 44 C. for twenty-fourhours and then at 100 C. for three hours with the following results:

Diall l g m phtbal ate Mhoun fl'lbours Per can;

o no 30 Do: M

50 Clear gel.

Example 3 Similar results were obtained with diethylene glycol maleateresin (acid number 32) and ethylene glycol maleate resin (acid number50) reacted with other diallyl esters:

Diallyl sebacate was found not to be appreciably soluble in ethyleneglycol or diethylene glycol maleate resins but was soluble in ions-chainglycol resins such as, for example, decamethylene glycol maleate resin.

Example 4 Ethylene glycol maleate resin (13 parts) was mixed withmethallyl alcohol (7 parts) and 0.2% benzoyl peroxide. At C. the massgelled in eight to ten minutes.

Example 5 To a mixture of about 40 parts of diallyl phthlate and about60 parts of ethylene glycol maleate resin (acid number 18), about 0.2%benzoyl peroxide was added. This was cast and cured in an oven at C. Aclear solid resin was obtained in four to five minutes.

Example 6 Approximately 250 parts of diallyl maleate were heated in abath. The temperatures of the bath as well as the solution wererecorded.

Terg glerature Temperature Total time elapsed, minutes lyl bath,

maleate, O. '0.

As soon as the exothermic reaction was appreached the material wasremoved i'rom further contact with heat for approximately fifteenminutes and then further heated. The mass was then allowed to stand atroom temperature and then distilled in vacuo. Approximately 60 parts ofcolorless viscous resin was obtained after the monomeric diallyl maleatehad been removed.

2 parts of the resinous diallyl maleate were dissolved in 1 part ofethyl fumarate and treated with 0.2% of benzoyl peroxide. Inapproximately ten minutes at 90 C. a cloudy hard resin resulted.

The resinous diallyl maleate was mixed with equal parts of ethyleneglycol maleate and treated with 0.5% of benzoyl peroxide. At 50 C.curing resulted in a hard clear resinous mass.

Other resinous substances containing a plurality of unsaturated groupssuch as allyl cellulose, methallyl cellulose, crotyl cellulose, etc.could be treated in a similar manner with reactive materials or withreactive resins.

Example 7 500 parts of phthalic anhydride, 103 parts of ethylene glycol,225 parts of allyl alcohol, 225 parts of toluene and 3.4 parts ofp-toluene sulfonic acid were heated in such a manner that the hot vaporspassed through a bubble-cap fractionating column before condensing. Thewater was separated and the other components returned to the still. Theheating was continued for approximately 16 hours. The mass was thenheated in a low vacuum to remove the low bolling constituents and thenin a higher vacuum (4 mm.). The bath around the flash was maintained atapproximately 180 C. for 2.5 hours to remove volatile materials.

The residue remaining was a soft fluid viscous resin of acid number of38.

One part of the above resin was mixed hot with 1 part of alphapropyleneglycol maleate resin and treated with 0.2 parts of benzoyl peroxide. At120" C. rapid curing was obtained.

Example 8 Equal parts of diethylene glycol maleate resin (acid number32) and diallyl maleate were mixed with 0.02% cobalt naphthenate and0.2% benzoyl peroxide. At 100 C. films of this composition on glassdried to very hard brittle coatings in ten minutes. One hour at 90 C.was required to obtain similar coatings when diallyl succinate wassubstituted for the dlallyl maleate.

Example 9 Triegixylene Ethylene Diany] Result at 90 C. at-

p thalid gg maleate iurnarlc resin 11 min. 20 min.

Pom Parts Parts 60 40 Tack-free Dry. 30 30 40 .do Do. 50 40 Tacky Do.

Example 10 Compositions similar to those of Example 9 were made usingthe'same proportions of diallyl maleate resin and catalyst. Thefollowing results 8 at C. were obtained with the resins indicated, theproportions being given in mol The resin with 80% fumaric acid is not soflexible as with 50% fumaric acid.

Example 11 60 parts of diallyl maleate were mixed with 40 parts ofdiethylene glycol phthalic-maleic resin (50% phthalic50% maleic) Filmsof this mixture dried from the bottom but the top remained soft. Theaddition of linseed fatty acids to the resin, however, eliminated thistack.

For coating compositions too large a proportion of maleic acid in theresin should not be used it best adhesion and pliability is desired. Toeliminate the slight amount of surface tack, the alkyd resin may bemodified with a small amount of drying oil acids. Drying oils containinga number of unsaturated linkages should be used. The alkyl resin shouldpreferably contain a certain number of oxygen bridges to gel; goodsurface drying.

Example 12 Phthalic anhydride parts, triethylene glycol parts) andlinseed oil (15 parts) were heated in an atmosphere of CO: at C. foreight hours, resulting in an acid number of 31.8. To the cooled mixthere was added maleic. anhydride (98 parts) and ethylene glycol ('70parts) and the mixture was then heated eight hours at 115 0. under 00,.During the last fifteen minutes the gas was blown through quitevigorously to remove the volatile ingredients. After further heating at150 C. for five hours a. resin of acid number 20.3 was obtained.

This resin was dissolved in diallyl maleate in the ratio 60:40,respectively and 0.2% benzoyl peroxide and 0.05% cobalt drier wereadded. Films of this dried on tin at 99 C. in fifteen to twenty minutes.They were hard and resistant.

Example 13 46 parts of glycerol, 49 parts of maleic anhydride, 35 partsof linseed oil acids and 69 parts of undecylenic acid were heated to 180C. during about three hours. Compatibility did not occur and the massgelled. Upon the slow addition of the linseed oil acids to the hotmixture of the other ingredients compatibility was established. Theresin (12 parts) resulting from this reaction was dissolved separatelyin diallyl maleate (8 parts and also in toluene (8 parts) and treatedwith 0.5% benzoyl peroxide and 0.05% cobalt naphthe'nate and baked at 90C. The resin-diallyl maleate mixture dried in less than an hour whereasthe resin-toluene mixture required one and one half hours to dry.

Obviously, the mixture containing the reactive resin and reactivematerial containing the group can be mixed with lacquer ingredients andsolvents such as cellulose derivatives. The following exampleillustrates such a coating composition:

Example 14 Per cent Nitrocellulose 29.2 Ethanol 12.5 Ethyl acetate 58.3

One part of each of the above solutions was mixed with one part oftoluene and the mixture applied to tin. The him was baked for fortyllveminutes at 90 C. to yield a clear, glossy, hard film.

The following examples show molding compositions and shaped or moldedarticles comprising my polymerizable reactive mixtures: 1

Example 15 To 125 parts of cellulose filler (Novacel) about 22 parts ofdiallyl phthalate containing about 0.1- 0.2 part of benzoyl peroxide areadded and the resulting composition is placed in a suitable mixer, e.g.. a Banbury mixer, and agitated until homogenized. About 45 parts ofthe solution containing 75% of ethylene glycol maieate and 25% ofdiallyl phthalate are added and the entire mixture is ground for aboutminutes.

The resulting product is molded at temperatures of about 130-150 C. andat pressures up to about 8000 pounds per square inch. Small dish-likemoldings are produced at this temperature and pressure in about 3minutes.

Example 16 Parts Ethylene glycol maleate resin 50 Diallyl phthaiate 50Benzoyl peroxide 0.05

t-Butyi peroxide -1 0.4-0.5

into a hot mold.

Example 17 Parts Resin 1? 60 Diallyl phthalate Benzoyl peroxide 0.5

Resin "E is dissolved in the diallyl phthalate and the benzoyl peroxideis added. The above solution is coated onto glass fabric and placedbetween smooth platens. A pressure 01' about 10-15 pounds/sq. in. isapplied to the platens, in order to remove entrapped air. The assemblyis then heated at about 150 C. for about 2 hours. The platens areremoved and a still sheet results.

. 0 Using 2 plies of glass cloth, possessing the trade name mil-161"(sold by Owens-Corning Fiberglas Corporation) the following Physicalproperties were obtained using the above resinous composition:

Tensile strength (+25" 0.) 32900 27,100 pounds/sq. in.

The difierence in strength was obtained by cutting specimens parallel toand at right angles to the warp.

The modulus in bending values were:

9.6x 10 pounds/sq. in. at 40 C. 6.1x 10* pounds/sq. in. at -40 C. 9.6X10pounds/sq. in. at +25 C. 1.3x 10 pounds/sq. in. at +25 C.

Example 18 Parts Diethylene glycol fumarate 50 Diallyl phthalate 50Lauroyl peroxide 0.5

The above composition is cast between sheets of glass. A paper spacer ofapproximately 30 mils is used to separate the glass sheets. The resin isforced into this space by means of a lnrpodermic needle. The assembly ismaintained for about 1 hour at C. The assembly is cooled and placed incold water. A thin, flexible, hard sheet of resin resulted. Thecomposition is especially transparent since both sides of the sheet hadtaken the surface from the glass.

Such sheets of resin may be used directly or may be sealed onto othersurfaces and used as a coating. When such materials are to be used ascoatings, it is preferably to abrade one surface. This may beaccomplished mechanically or in the manufacture thereof by the use ofetched glass as one casting surface in the above assembly.

Example 19 A thin, flexible sheet may be prepared by using a formulationsuch as follows in the process outlined in Example 18.

Parts Resin "1" 60 Diallyl phthalate 50 Benzoyl peroxide 1 Resin "F" isprepared by heating 2 mols of sebacic acid, 1 moi f umaric acid andthree mols of ethylene glycol at about 200 C. until the acid number isabout 50.

A flexible sheet is formed which is similar to that obtained in Example10.

Example 20 In order to produce compound curved laminated forms, thefollowing procedure has been found satisfactory: Canvas or glass clothcut to size is impregnated with the reactive mixture employed in Example17. The layers of impregnated resin are placed in an appropriate formand a vacuum applied, suitably with a rubber bag. The

assembly is then heated for approximately hours at 110 C.

Canvas is impregnated with the above solution and the excess, if any, isremoved by passing the impregnated canvas through squeeze rolls.

The impregnated canvas is then placed in an oven at about 80 C. untilthe resin has been partially converted to the infusible, insolublestage. This operation requires approximately 2-3 hours. The impregnatedcanvas should be molded immediately or if allowed to stand for any time,precautions should be taken to avoid exposure to air or oxygen.

The sheets of impregnated canvas are cut, stacked and molded under heatand pressure at about 2000-3000 pounds per square inch and attemperatures around 125 C. for approximately 4 hours, thereby producinga laminated cloth plate of very high transverse strength.

Alternatively, cut canvas sheets may be impregnated with the abovecomposition without the use of the volatile solvents, alcohol andtoluene.

The solution of dialiyl phthalate and alkyd resin is applied to canvasusing equal weights of canvas and reactive composition. The assembledsheets are placed between platens and placed in a press. A pressure ofabout 50 pounds/sq. in. is applied and the mass cured at 150 C. for 1.5hours. A still? cured resinous material results. Paper may beimpregnated in a similar manner. For example, a composition containingapproximately 45-50% resin has a transverse strength of aboutl6,000-19,000 pounds/sq. in. This laminated plate is particularlysuitable for use in production of gear wheels because of the hightransverse strength and since it may be machined easily.

Example 22 Parts Ethylene glycol maleate resin 60 Diallyl maleate 40Benzoyl peroxide 0.7 Cobalt naphthenate 0.04

This mixture is used to impregnate canvas and the impregnated canvas isheated at about 80 C. for around 30-35 minutes in an oven. The materialis then cut, stacked and molded at a pres sure of about 2500-3000pounds/sq. in. at a temperature of about 125 C. and for approximately 3hours. The molded plate thus produced has a transverse strength of about17,000 pounds/sq. in. and it contains about 40 per cent resin. Thestrength may be increased and the electrical properties may be improvedsomewhat by curing the resin at lower temperatures, e. g., 105 C. and atordinary atmospheric pressures. This, of course, requires acorrespondingly longer time for the conversion to the infusible,insoluble stage.

Example 23 Parts Resin G 50 Diallyl maleate 50 Benzoyl peroxide 7 Thiscomposition is applied to paper on 8. tu e rolling machine, the machinecomprising suitable rollers for paper and a means for distributing auniform coating of resin on the paper. After the resin-impregnated paperhas been rolled, the roll is cut, stacked and partially cured (i. e.,polymerized) at about 110 C. and then molded at somewhat highertemperature, e. g., 120-130 C. at a pressure of about 2000 pounds/sq.in. The resulting molded plate has good electrical properties and it hasexcellent transverse strength. If desired, cylindrical moldings can beproduced by suitable modification of the apparatus and process.

Resin G is prepared by heating at about 180 C. under an inert atmosphere650 parts of phthalic anhydride, 420 parts of maleic anhydride, 800parts of triethylene glycol, 410 parts of ethylene glycol and 180 partsof linseed oil fatty acids in a suitable reaction chamber provided witha reflux condenser which has a water trap to separate the water formedduring the esteriflcation from the condensate. The mixture is heated forabout 4-12 hours or until a relatively low acid number is obtained, e.g., about 20.

Example 24 60 parts of diethylene glycol furnarate and about 40 parts oftriallyl phosphate are blended together and about 0.2% of benzoylperoxide is added. Castings of the resulting polymerizable compositionmay be rendered substantially insoluble and substantially inusible byheating at a temperature of about -120 C. for around 1-4 hours or more.

Example 25 50 parts of diethylene glycol maleate, about 50 parts oftriallyl phosphate and 0.2 part of benzoyl peroxide are mixed together.A small casting completely poiymerizes at about 50 C. in about 16 hours.

I Example 26 10 parts of triallyl tricarballylate are mixed with 10parts of diethylene glycol maleate resin and 0.4% benzoyl peroxide, Theresulting reactive mixture is heated in the form of a small casting forabout 40-60 C. for about 24 hours and then at about C. for severalhours. A hard clear casting is obtained.

Example 27 10 parts of diallyi sebacate are mixed with 10 parts of aresin obtained by esterifying 1 mol of diethylene glycol with about 1mol of a mixture including fumaric acid and sebacic acid, the molalratio of fumaric acid to sebacic acid being about 4:1. About 0.2% ofbenzoyl peroxide is added to the resulting mixture. Films of thepolymerizable mixture may be cured by baking at about C. for from 1-4hours or more. Clear. flexible films which are substantially infusibieand substantially insoluble are obtained.

Vrscosrrr ADJUSTMENT or Rmc'rrva Mrx'ruas It is sometimes desirable toreduce the viscosity of my mixtures of reactive resin and reactivematerial-containing the CH2=C group, as for instance, when a veryviscous resin is to be used for coating. It is possible to do this byadding an esterification catalyst, e. g., p-toluene sulionic acid andthen heating until the viscosity goes down. The mechanism of this changeis probably reesterification. This is also useful when the compositionis to be baked at high temperature, under which conditions the reactivematerial would be lost in part by evaporation. If this 13 thinningprocess is carried out, the reactive material is combined with the resinby reesterification and is not lost. It is also desirable to add apolymerization inhibitor before the heating or "thinning" process.

Example 28 A resin made by esteriilcation at 150 C. of 294 parts ofmaleic anhydride, 121 parts sebacic acid. 227 parts of ethylene glycol,32 parts of linseed fatty acids and 3.6 parts of p-toluene sulfonic acidwas mixed with diallyl maleate in the ratio of 80 parts of resin and 40parts of diallyl maleate, 0.01% p-toluene sulfonic acid added. and themixture heated in an oil bath at 90 C. for five hours. The viscositydecreased from to 8 poises.

In casting or molding operations using a mixture of a reactive resin andreactive material containing the CH2=C group, it may sometimes bedesirable to body the reactive mixture before adding the catalyst inorder to out down the induction period which would otherwise be toolong. This may be done by heating a mixture of resin and reactivematerial from about 70 C. to about 110'C., preferably at about 90 0.,for sufficient length of time to substantially reduce the inductionperiod. This time will vary with each resinreactive material combinationwith the initial viscosity and other such factors but may be determinedby observation of the rise of viscosity. The heating should continueuntil the viscosity begins to rise rapidly. A general rule fordetermining the heating time is to heat the mixture until the viscosityis about two to three times the initial viscosity.

After the bodying operation is carried out, the polymerization catalystis added to the mixture and the whole subjected to polymerizationconditions. The use of liquid peroxides instead of solid peroxides is anadvantage after bodying the resin mixture since it is difllcult to getthe solid peroxides dissolved rapidly enough. Peroxides of the coconutoil acids, tertiary butyl peroxide and ascaridole are suitable liquids.

By the use of this process the induction period is cut down fromapproximately Va to A; the time that is required when the bodyingprocess is not used. Even greater reductions are obtainable with somemixtures.

In bodying reactive mixtures containing the reactive.resin and areactive material containing the CH2=C group wherein the proportion ofreactive material is greater than about 30 the viscosity rise is sosudden that it may be somewhat difllcult to control it. Accordingly. ifit is desired to body a resin-reactive material mixture containing morethan 30% of reactive material, an alternative procedure is used. By thismethod one first bodies a mixture containing only 30% of reactivematerial. Then a small portion of additional reactive material is added,for example, suflicient to make the reactive material concentration 40%and then this is bodied. If still more reactive material is desired,another small portion of reactive material is added and the bodingprocess repeated. This process is repeated until the desiredconcentration and viscosity is obtained.

Annrrron or Innrsrrons One of the dimculties in the use of the com-'polymerization will usually take place even at room temperature within acomparatively short time. Moreover, when it is desired to cure thecompositions very rapidly under heat and pressure, the reaction becomesat times so vigorous that it cannot be controlled. In order to overcomethese diiilculties it has been found advisable to incorporate a smallproportion of a polymerization inhibitor in the mixture of resin andreactive material. When it is desired to use this mixture, a smallpercentage of the polymerization catalyst is added, suflicient toovercome the effect of the inhibitor as well as to promote thepolymerization. By careful control of the concentrations of inhibitorand cataLvst. a uniform product is obtainable with a good reactionvelocity. Upon subjection of this mixture to polymerization conditionssuch as heat, light or a combination of both. and with or withoutpressure, an iniusible, insoluble resin is produced which has many moredesirable characteristics than the resins produced by the polymerizationof mixtures not containing the polymerization inhibitor such as, forinstance, the lack of fractures.

Suitable polymerization inhibitors for this reaction are phenoliccompounds especially the polyhydric phenols and aromatic amines.Specific examples of this group of inhibitors are hydroquinone,benzaldehyde, ascorbic acid, isoascorbic acid, resorcinol, tannin, sym.di, beta naphthyl p-phenylene diamine and phenolic resins. Sulfurcompounds are also suitable.

The concentration of inhibitor is preferably low and I have found thatless than about 1% is usually suillcient. However, with the preferredinhibitors I prefer to use only about 0.01% to about 0.1%.

The inhibitor may be incorporated in the reactive resin-reactivematerial combination (either before or after bodying) or it may be addedto the original reactive resin before or during the esterification ofthe said reactive resin. By adding the inhibitor before theesteriflcation it is sometimes possible to use an inhibitor which wouldotherwise be substantially insoluble in the reactive resin-reactivematerial composition. By adding the inhibitor to the unesterifiedmixture the inhibitor may become bound into the resin upon subsequentesteriflcation.

Example 29 Resins were made up of the following compositions byesteriflcation for the same length of time at 0.:

Ingredients Resin No. l Resin No. 2

Maleic snbydride Ethylene glycol Benzaldehyde Rssc'nvs RESIRS AND THEIRPnsrsas'rron Reactive resins suitable for polymerization with reactivematerials containing the CH2=C group in accordance with the teachings ofour invention are those which contain a plurality of alpha.

beta enal groups. The simplest members of this group are those producedby the esterification of an alpha, beta-unsaturated organic acid with apolyhydric alcohol.

The preferred polyhydric alcohols are those which contain only primaryhydroxyl groups since the presence of secondary hydroxyl groups may makeit difllcult to obtain rapid esterification. The glycols are generallypreferable. If colorless resins be desired or if optimum electricalproperties be desired, it is preferable to use glycols which do not haveany oxygen bridges in their structure since the presence 01' oxygenlinkages may lead to the formation of color bodies during thepreparation of the resin. By the use of glycols which do not contain theoxygen bridges clear colorless resins may be produced. On the otherhand, oxygen bridges may be desirable if the resin is to be used incoatings as they cause films to dry faster.

The particular choice of glycol or other polyhydric alcohol used inpreparing the resin is governed mainly by the physical propertiesdesired 01 th intermediate and final polymerization products, especiallyhardness, impact resistance, distensibility, refractive index, adhesion,compatibility relationships, etc., including also solvent, water,alkali, acid or chemical resistance in general.

The alpha, beta unsaturated organic acids which I prefer to use inpreparing th reactive resins include maleic, fumaric, itaconic andcitraconic although other similar acids could be substituted such asmesaconic acid, aconitic acid and halogenated maleic acids such aschlormaleic acid and any of the foregoing could be substituted in partwith acrylic, beta benzoyl acrylic, methacrylic, zi -cyclohexenecarboxylic, cinnamic, and crotonic acids. Obviously, various mixtures ofthese acids can be used where expedient.

The reactive resins may be modified with other substances which are usedin alkyd resins, i. e., monohydric alcohols, monobasic acids or dibasicacids, e. g., phthalic acid, succinic acid, glutaric acid, adipic acid,azelaic acid, sebacic acid, etc. which do not contain groupspolymerizably reactive with respect to organic substances containingCH2=C groups. These modifying agents are usually used as diiuents orplasticizers, chemically combined in the resin. The use of a smallproportion of the saturated dibasic acids generally improves themechanical properties of the resins after copolymerization with thematerial contain ing the CH2=C group.

The reactive resins may be prepared from polyhydric alcohols other thanthe glycols or from mixtures including a glycol and a higher polyhydricalcohol. Examples of these are glycerol, pentaerythritol, etc.Polyhydric alcohols containing more than two hydroxyl groups react veryreadily with the alpha, beta unsaturated organic acids. Consequently itmay be preferable to use some monohydrlc alcohol in conjunction with thealcohols which contain more than two hydroxyl groups or else somemonobasic acid may be used.

It is also possible to introduce initially into the resin structure acertain number of groupings of the type CH==C through the use ofunsaturated all-ryl compounds. One way of accomplishing this, forexample is by direct esterification of an unsaturated alcohol containinga CH2=C group. Examples of such alcohols are allyl alcohol and methallylalcohol.

While the reactive resins may be modified in the same general manner asother alkyd resins, it is preferable to have at least 20% polyhydricalcohol in the reactive mixture and at least 25% polybasic acid in saidreactive mixture. If a monohydric alcohol or a dibasic acid which doesnot contain polymerizabl active groups with respect to organicsubstances containing the CH2=C groups be used, the proportion 01' suchsubstances will depend on the properties required of the polymerizedreactive material-reactive resin mixture. By the use of a relativelylarge proportion of a polymerizably active dibasic acid, e. g., maleic,in the reactive resin, a hard, tough polymer is produced upon subsequentreaction of said reactive resin with a reactive material containing theCH2=C group. On the other hand, if the reactive resin is obtained from arelatively small proportion of polymerizably active dibasic acid and arelatively large proportion of acids which do not contain groupspolymerizably active with respect to organic substances containing CH2=Cgroups, a softer and more rubbery resin results upon polymerization witha reactive material containing the CH2=C group. The same eiiect isproduced by the introduction of other inactive ingredients. By varyingthe ingredients and the proportions of the ingredients, resins may beobtained having propertie desirable for almost any particular use.

The unsaturated alkyd resins employed in accordance with my inventionare preferably those having an acid number not greater than 50 althoughin some cases resins having an acid numher as high as may be desirable.Generally the acid number should be as low as possible, but this issometimes controlled by practical considerations of operation such astime, temperature and economy.

The resins should be so formulated that the carboxyl groups of the acidsare reacted with the theoretical molal equivalent of the hydroxyl groupsof the alcohols. In this connection it is to be noted that the hydroxylgroups of modifying alcohols as well as the carboxyl groups of modifyingacids should be included with the hydroxyl groups and carboxyl groups ofthe principal reactants, the polyhydric alcohol and the alpha, betaurmaturated polycarboxylic acid, respectively.

If it be desirable to introduce lower alkyl groups into the resin, thismay be done by using maleic esters of monohydric alcohols, e. g., ethylmaleate. The alkyl ester will then be united with the resin bypolymerization. This could not be accomplished with the saturated typeof alkyd, e. g., phthalic acid esters of polyhydric alcohols.

Resins which contain a plurality of alpha. beta enal groups aresensitive to light, heat and polymerizing catalysts. Since oxygen tendsto cause these resins to polymerize, it is desirable that the resinsshould be made in the absence of this substance, especially whencolorless resins are required. The exclusion of oxygen and polymerizingcatalysts is desirable during the preparation of the resin and thepresence of dissolved oxygen in the original reactants is alsopreferably avoided. Moreover, dust and extraneous particles thatreagents may pick up usually should be removed, especially if colorlessresins are desired. One manner in which the dissolved gases and otherextraneous impurities may be removed is through the distillation of theingredients into the reaction chamber in the absence of air.

In order to keep oxygen from contact with the reactants an inert gassuch as carbon dioxide or nitrogen may be introduced into the reactionchamber. This may be done either by merely passing the gas over thesurface or by bubbling the gas through the liquid reactants. In thelatter instance it may be made to perform the added function ofagitating the mixture thus eliminating the necessity for mechanicalagitation. The inert gas will also carry away at least part of the waterformed and toward the end of the reaction it can be used to carry awaythe reactants still remaining unreacted. Upon separation of the watervapor the used carbon dioxide or other inert gas would be particularlysuitable for making high grade colorless resins since any residualreactive impurities such as oxygen would have been removed in itspassage through the first batch of resin reactants.

The effect of light is not so important if the reactants are purifiedand the reaction carried on in an inert atmosphere as outlined above.However, as an added precaution the esteriiication may be conducted inthe dark. It is also advisable to avoid local overheating anddiscoloration is minimized if the reaction is conducted below atemperature of about 200 C. To avoid overheating it is advisable toraise the temperature slowly at the beginning, especially if ananhydride be used since the reaction between an anhydride and an alcoholis exothermic.

The preparation of the reactive resins is illustrated in the followingexamples, the reactants being given in parts by weight.

PREPARATION OF RESIN "A" 98 parts of freshly distilled maleic anhydridewere reacted with about in excess of equimolecular proportions offreshly distilled ethylene glycol (68 parts) at about 170-175 C. Anexcess of ethylene glycol is preferred because of its high volatility.The mixture is continuously agitated and carbon dioxide is introducedinto the reaction chamber during the reaction thereby blanketing thesurface of the reactants. After eight to twelve hours a clear,water-white resin is produced with an acid number of 35-50.

Panraaa'rrou or RESIN B 1200 parts of maleic anhydride were mixed with1023 parts of alpha propylene glycol (equivalent to one mol of each plusapproximately glycol). This mixture was heated with agitation in aninert atmosphere at 150-165 C. After about four hours the resin turnedopaque on cooling. After about eleven hours heating, a resin is obtainedwhich is somewhat brittle at room temperature and the acid number isbetween 35-50.

Pnnnnarrou or Ruacnvn Rnsm Azno rnorrcaur Since the viscosity of theresin frequently becomes quite high if the esteriflcation is carried toa low acid number, it may be desirable to produce the resin underazeotropic conditions. Accordingly, the esteriflcation is conducted inan organic solvent which dissolves the reactants as 10% of the well asthe resultant resin and which is preferably substantially insoluble inwater. Examples of these are: benzene, toluene,xylene, chloroform,carbon tetrachloride, ethylene dichloride, propylene dichloride,ethylene and propylene trichlorides, butylene dichloride and trichlorldeand also higher boiling solvents such as cresol and methyl cyclohexanonealthough some of these may tend to darken the resin. The mixture isrefluxed in such a manner as to separate the water formed by theesterification. Much lower temperatures are used than are used under theconditions outlined in Examples 17-19. Suitable temperatures rangebetween -145 C., for example, for the lower boiling members of the groupof solvents set forth above. Obviously, this will vary with differentsolvents and with different concentrations of solvent. The range ofpreferred concentrations for the inert solvent is from about 25% toabout 50%. An esteriflcation catalyst is usually necessary because acomparatively low temperature is employed. Examples of these are thymolsulfonic acid, d-camphor sulfonic acid, naphthalene sulfonic acid andp-toluene suifonic acid. Obviously other known esteriiication catalystscould be used. A resin having any particular acid number if madeazeotropically will usually have a lower viscosity than one of thecorresponding acid number not made azeotropically.

Pnnnuurron or Rasm D 98 parts of maleic anhydride, (vacuum distilled),106 parts of diethylene glycol (vacuum distilled) about parts ethylenedichloride and about 3 parts d-camphor sulionic acid were mixed in areaction chamber. The heating was conducted in an oil bath maintained atl30-145 C. for nine hours. The distillation temperature began at about90 C. but gradually rose during the heating. The apparatus was 50arranged that the water would be separated from the reflux. A lightyellow resin with an acid number of about 19.8 was produced afterdriving oil? the volatile ingredients including the ethylene dichloride.

Similar results were obtained using thymol sulfonic acid andapproximately the same proportions except that only about 148 parts ofethylene dichloride were used. A resin of acid number 11.3 was obtained.

The resins prepared in the manner illustrated above are merely exemplaryof the reactive resins which I contemplate using for reaction with amaterial containing the CH2=C group in the practice of my invention.Other resins of the same type may be prepared in a similar manner.

Among these resins the following may be employed in place of part or allof those mentioned above: ethylene glycol fumarate, diethylene glycolfumarate, alpha propylene glycol maleate, polyethylene glycol maleates(e. 5., hexaethylene glycol maleate), polymethylene glycol maleates (e.g., decamethylene glycol maleate) octadecam diol fumarate. the maleicesters; of 2,2-dimethyl propanediol-L3, of 1,3-butanediol, of1,2-propanediol and of 2-ethyl. 2 butyl butanediol-l,3, glycerol maleateundecylenate, triethylene glycol chlormaleate, triethylene glycolterpene maleate (derived from the interaction of 5a mol of terpene and 1mol of maleic in the presence of excess of terpene).

When a resin is treated with a reactive material containing the CH2=Cgroup, the material may or may not dissolve the resin depending on thechemical nature of both the material and the resin. If the resin beincompatible with this reammo active material, chemical interaction ofthe type described cannot occur in that compatibility has not beenestablished. Under these conditions another solvent may then beintroduced as an additional constituent. If the solvent is inert, itplays no part in the reaction but is so selected that both the reactivematerial and the resin are soluble yielding a homogeneous system oireactive material, inert solvent and resin. This invention relates tocompatible combinations of a reactive resin and a reactive materialcontaining the CH:=C group. Such combinations may be obtained by the useof inert blending solvents where necessary although the use of onlyreactive materiaiscontalning the CH2=C group which act as solvents ispreferred The terms compatible and homogeneous as used in thespecification and claims are intended to indicate a system, theconstituents of which are uniformly distributed throughout the wholemass, and when applied to solutions, to indicate that these may beeither true solutions or colloidal solutions as long as they aresubstantially stable. 7

when a reactive resin and a reactive material containing the CH2=C groupundergo chemical reaction, certain possibilities arise. The reactiveresin and reactive material may combine in such a manner as to lead tothe formation of a resinous colloidal entity and the end-product isclear, glass-like and homogeneous. Alternatively, the reactive resin andthe reactive material may interact in such a manner as to yieldcolloidal entities wherein varying degrees of opacity or colloidalcolors result. The end-product under these conditions may be partiallytranslucent or opaque.

The final resin composition is obtained by dis solving a resincontaining the alpha, beta enal groups in a reactive material containingthe group C=CH:. The chemical reaction which is believed to take placeis that the reactive material combines with the resin at the points ofunsaturation yielding a less unsaturated system which is essentiallyinsoluble and infusible. rdinarily when a resin is dissolved in asolvent, the changes which occur are physical in nature. The resin maybe isolated from the solvent mixture chemically unchanged. In thepresent invention, however, the combination oi the reactive materialcontaining the CHz=C group which acts as the solvent and reactive resinbecomes an inseparable entity. the original ingredients not beingremoved by the solvents for the original ineredients.

Through the use of a small amount or reactive alkyd resin dissolved in alarge amount of reactive material containing the CH==C roup. the finalcomposition contains not only the ester groupings which were originallypresent in the alkyd resin but also the carbon-to-carbon molecular bondswhich link the reactive material and the reactive resin. Through the useof a small amount of resin and a large amount oi reactive material, thecomposite resin is no longer soluble in those inert solvents wherein thereactive material resinifled alone would dissolve. Under long exposur tothe inert solvent, the composite resin will tend to imbibe a certainquantity of inert solvent but it does not possess the solubility of thereactive material when resinifled alone. This property is a distinctadvantage in that the physboth ingredients: and third,

20- ical contour of an object made of the polymerized resin is not lostthrough solution.

Comparison of the softening point of the reactive material co tainingthe CHz=C group alone and of the itching point of the composite resinformed through interaction 01 the resin and reactive material shows thatthe softening point of the latter has been raised. The softening pointmay be increased very markedly depending upon the ratio of resin used inthe composition,

In general the softening point of resins has a distinct bearing on theirbehavior at room temperature as well as at elevated temperatures.

Where the softening point is too low, difilculty is encountered in thatarticles made from the resin slowly lose their shape. In large articlesthe eifect becomes very noticeable. A point when too high, on the otherhand, results in a composition which will not soften sufiiciently in amold. Roughly, three types of compositions exist with respect to theratio of resin to reactive material containing the CHz=C group. First, alarge amount of reactive material and a small amount of resin; second,substantial quantities of a large amount of resin and a small amount ofreactive material. The second composition when iully cured possesses nosoftening point. The first and third varieties of composition when curedmay, under high temperatures and pressure, be made to fiow li htly.

The composition obtained from substantial quantities of both reactivematerial containing the CH==C group and reactive resin in the curedstate may be machined, turned on a lathe, sanded and polished and usedin general as a turnery composition. The absence of softening rendersthe material particularly adaptable to this purpose. In that it isunfiowable, it may be machined without danger or softening and gummlngtools. Moreover, such a composition may, if desired, be obtained inlarge blocks My resins may be utilized in: moldings, with or withoutfiller; laminated materials as the bonding agent; adhesives; coatingcompositions for use in finishes for wood, metals or plmtics, or in thetreatment of fibrous materials such as paper, cloth or leather; asimpregnating agents for fibrous materials; as assistants in dyeing, etc.

In order to use the composition for molding, it may be necessary toprevent the composition from curing too fast. During the change from aliquid to a hard resin, varying stages of hardness exist and byinterrupting the reaction at a definite point, the material may then bep aced in a form and hardened under heat. Sheets of resin may betwisted, or made to conform to a pattern, and then subsequently cured inthe shaped form by heat alone.

One manner in which this may be accomplished is to polymerize thereactive resin and reactive material containing the CH1= group withoutcatalysts until the material is no longer fluid but still not completelycured. By grinding this partially polymerized material a moldingcomposition is obtained which can then be shaped under heat andpressure.

Example 28 A mixture of about 40 parts by weight or diallyl phthalateand about 60 parts by weight of ethylene glycol maleate resin (acidnumber 18) was mixed with 0.2% benzoyl peroxide. This would ordinarilyel in five to six minutes at C. The mixture was prewarmed for twominutes at success 21 90 C. and poured into the mold, the manure raisedto 2000 pounds for about two minutes and then lowered to 1000 pounds.The mold was opened after eight minutes to yield a clear hard disk.

Example 29 A mixture of equal parts by weight of butylene glycolfumarate, (prepared by heating molar quantities or butylene glycol andfumarlc acid at about 175 C. until the resin has an acid number oi about50) and diallyl phthalate is treated with 0.5% of benaoyl peroxide andpoured into a mold, the sides of which are two sheets of plate glassspaced Ya inch apart. The assembly is heated for about ti hour at 100C.Under these conditions, a flexible sheet is formed.

The sheet may be distorted and bent into various forms. By furthercuring in the bent form the resin hardens and assumes the term imposed.

One procedure is as follows: A mandrel was lightly covered withglycerol, the flexible sheet is bent over the mandrel and the resin iscovered with glycerol. A thin sheet of metal is then superimposed on theassembly and secured mechanically. The entire mass is heated in an ovenfor 1 hour at 150 C. A hardened shaped mass results.

The glycerol is used to maintain the original clear surface. It isparticularly useful where one surface is glass since the cured resin mayadhere very tenaciously to glass.

All types of simple curves can readily be fashioned. Compound curves aremore difficult to produce since the resin in the semi-cured stage may bedistensible to only a limited extent.

To produce moldings or laminated materials combinations oi reactiveresin and reactive material containing the CH2=C group may be mixed withone or more of the various fillers, e. g., wood flour, wood fiber, paperdust, clay, diatomaceous earths, zein, glass wool, mica, granite dust,silk flock, cotton flock, steel wool, silicon carbide, paper, cloth ofany fiber including glass, sand, silica flour, white, black or coloredpigments, etc. Such mixtures may be partially polymerized, ground andmolded. n the other hand, the liquid composition may be bodied andintroduced directly into a mold and polymerization from a viscous liquidto a solid resin conducted in one step.

In that the composition of reactive resin and reactive material isinitially quite limpid, it may be used for impregnating various porousobjects or employed as a coating composition.

If the polymerizable compositions are to be molded under low pressure(e. g., 0-50 pounds/sq. in). the composition may be employed withoutbodying or partial polymerization.

The liquid polymerizable mixture may be introduced in a positive moldwithout any filler. In this instance, however, the reaction becomesquite exothermic but this may be conveniently controlled by the additionof a suitable polymerization inhibitor.

The ratio of reactive material containing the CHa=C group to reactiveresin in the final composition will not only have a bearing on thesoftening point and on methods of working the resin but on various otherphysical properties, e. g., light transmission, scratch resistance,indentation hardness and are resistance. By a judicious selection of theratio of reactive material to reactive resin a composition best suitedto these varying needs of industry may be fabricated.

The methods by which the reactive material containing the CH==C groupmay be made to combine are various. Heat, light or catalysts may be usedor combinations of these, or a combination of heat and pressure. Anysuitable method of heating may be used including the application 01'high frequency electric iields to induce heat in the reactive mixture topolymerize the latter.

During the transformation or the soft, limpid resinous composition to ahard massive structure, various stages occur which may be roughlyseparated as follows: first, the induction period wherein the materialremains as a sol which slowly increases in viscosity: secondly, thetransformation of the so] into a gel; and third, the hardening of thegel. During the transformation of the sol to a gel. an exothermicreaction occurs which may be very violent if uncontrolled. Moreover, thegel has relatively poor heat conductivity resulting in heat beingtransferred poorly through the mass. not only external heat but the heatthat is generated during chemical reaction. cognizance has to be takenof these features in the hardening of the composition, particularly inthe casting or molding of large blocks.

Light when used alone causes a relatively long induction period andduring the transformation 01' the sol to the gel requires cooling toovercome the exothermic reaction especially when a poweriul source oflight is used for final curing. Using heat alone, gelation occursreadily enough at appropriate temperatures but since the gel, whenformed, has poor heat conductivity. fracturing may occur in the laststage. Through the use of heat and catalyst, the reaction may becomevery violent unless the heating is carefully controlled.

Various combinations oi these three factors may be used to bring abouthardening of the mass. Mild heating of the reactive resin and reactivematerial containing the CHa=C group with or without inhibitors bringsabout a very gradual increase in viscosity which may be controlled quiteeasily and readily. When the solution has taken on an appropriateconsistency, then accelerators may be introduced and heating conductedat a very much lower temperature. Mild heating may first be used and themass then exposed to light. Use of superoxides and light is veryeflective. In other words, through the use of initial heating orbodying, the induction time may be decreased markedly.

While I have specifically described the reaction of mixtures of areactive resin and a reactive material containing the CH2=C group in theliquid state I am not precluded from reacting the reactive material inthe vapor state with the resin. Compositions containing a reactive resinand a reactive material containing the CH=C group are originally liquidcompositions and by proper treatment at relatively low temperature theycan be converted into hard masses. The wide divergence of the propertiesof such compositions enables them to be used in a variety of differentways. In the liquid form they may be used as an adhesive, impregnatingagent or as a surface coating. In that the hardening does not dependupon evaporation, the liquid may be applied to the surfaces desired withthe reactive resin mixed with the reactive material containing the CH2=Cgroup which acts as the solvent and combining in situ to form ahomogeneous adhesive. Such an adhesive can be used for bringing diversesubstances together, wood, metal, glass, rubber, or other resinouscompositions such amass:

23 as phenolic or urea condensation products. As a surface compositionin the liquid form, softening agents, cellulose others or esters couldbe added as well as natural or artiiicial resins. and the hardeningbrought about through catalysts such as cobalt salts, oxygen liberatingsubstances or hardening could be accomplished with light. Since thesecompositions dry from the bottom rather than from the top, the latterfrequently remains tacky for a relatively lengthy period. In order toovercome this, drying oil fatty acids, e. g., linseed oil fatty acidsare added to the esteriflcation mixture in making the original reactiveresin and this will cause the top surface to dry quickly upon subsequentpolymerization with a reactive material containing the CH==C group. Inthis way a coating composition is obtained which dries both from top andbottom.

The liquid resinous composition, moreover. may be cast or molded andafter hardening may be isolated as a finished product, or could be cut,turned and polished into the desired finished product. Provided thesurface oi the mold is highly polished. the resinous substance wouldacquire a clear, smooth finish from the mold. The compositions soobtained being insoluble are not easily attacked by solvents and beinginfusible may be worked with ordinary wood working or metal tools. Theartificial mass can be cut. turned on a lathe, polished and sandedwithout superficial softening and streaking.

Obviously natural resins or other synthetic resins may be admixed withthe resins of this invention in order to obtain products suitable forparticular purposes. Examples of these are shellac, cellulose esters andethers, urea resins, phenolic resins, alkyd resins, ester gum, etc. Theresins of my invention may also be mixed with rubber or syntheticrubber-like products if desired.

In that many of these resins or originally transparent and free ofcolor, they may be colored with suitable dyes to a wide variety oftransparent soft pastel shades. An example of a suitable dye is SudanIV. Darker shades may be obtained. if desired. e. g., with nigrosine.

It may be desirable in some instances to form a copolymer of one or moresubstances containing the group CH2=C and at least one polymerizableunsaturated alkyd resin and, after molding or casting this into anydesired shape, to apply a coating of a harder copolymer to the outside.thus obtaining the same eil'ect as is obtained in the metallurgicalfields by case hardening. Similarly, inserts may be filled with a hardresin in order to act as bearing surfaces or for some other purpose-Such coatings or inserts adhere tenaciously and appear to becomeintegral with the original piece. In order to secure the best results inmanufacturing such products, it is desirable to first abrade the surfaceof the article before the application of the harder film. During thecuring operation, the abrasion marks disappear. This treatment is alsoof considerable importance since it may also be used to refinisharticles which might have been marred in use.

Many of the advantageous properties of the resin resulting from thepolymerization of mixtures containing reactive materials containing theCH1=C group and reactive resins are apparent from the foregoingdisclosure. Several important advantages are now to be set forth.

In molding and casting operations curing takes place either in thepresence or absence of air very rapidly. This is of great importance inouring large blocks. Other alkyd resins require a very much longer timeto cure in large blocks, 1. e., many months, whereas the composition ofa reactive resin and reactive materials containing the =C group requireonly a few days at the most.

Another important advantage is the fact that the reactive materialcontaining the CH=C group which acts as the solvent combines with theresin leaving no residual solvent and giving no problems as to solventremoval.

One of the outstanding advantages of these resins is quick curing timewhich renders them available for inJection molding, blow molding, andextrusion molding.

Castings which are polymers of such substances as methyl methacrylate.for example, frequently contain bubbles which are formed in the lowerpart of the casting. Inasmuch as the present invention is directed tosystems wherein the polymerization proceeds from the bottom to the top,no bubbles are trapped in the casting.

Similar advantages are present in coating operations such as the lack oishrinkage of the film due to loss of solvent because of the combinationbetween the reactive resin and the reactive material containing theCH2=C group which acts as the solvent. Furthermore, the compositiondries from the bottom, there are no bubbles from the solvent and thereis no water driven off. A clear bubble-free, impervious coating is,therefore. more readily obtainable with the combinations of a reactiveresin and reactive material containing the CH2=C group than with othercoating compositions. Since there is no solvent to be removed and sinceair is not needed to dry the compositions, relatively thick layers maybe applied in one operation.

This application is a continuation-in-part of my copending applicationsSerial Nos. 248,536, filed December 30, 1938; 349,240, filed August 1,1940; and 487,034, filed May 14, 1943.

Obviously many other reactants and modifications may be used in theprocesses outlined in this specification without departing from thespirit and scope of the invention as defined in the claims.

Iclaim:

l. A polymerizabie composition including (1) an unsaturated alkyd resin(2) triallyl phosphate and (3) a catalyst for accelerating thecopolymerization of (1) and (2).

2. A polymerizable composition comprising (1) triallyl phosphate, (2) apolymerizable unsaturated alkyd resin compatible with the said phosphateof (1), and (3) a. catalyst for accelerating tlzie copolymerization oithe materials of (1) and 3. A composition comprising the product ofpolymerization of a polymerizable mixture including (l) triallylphosphate and (2) an unsaturated alkyd resin, said materials of (l) and(2) being copolymerizable and compatible.

4. A composition comprising the product of polymerization of apolymerizable mixture of copolymerizabie, compatible materials includingl) triailyl phosphate and (2) an unsaturated alkyd resin obtained byreaction of ingredients comprising a dihydric alcohol and an alphaunsaturated alpha beta dicarboxylic acid.

5. A composition comprising the product of polymerization of apolymerizable mixture including (1) triallyl phosphate and (2) a maleicester of a poiyhydric alcohol, said materials of 25 (1) and (2) beincoopolymerizable and compatible.

6. As a new product, a resinous interpolymer obtained byinterpolymerization of a mixture of copolymerizable materials consistingof diethylene glycol maleate and triallyi phosphate.

'7. The method of producing new synthetic compositions which comprisespolymerizing a polymerizable composition comprising (1) triallylphosphate, (2) a polymerizable unsaturated alkyd resin compatible withthe said phosphate of (l), and (3) a catalyst for accelerating thecopolymerization of the materials oi (l) and (2).

8. The method of producing an insoluble and ini'usible resinouscomposition which comprises heating a mixture of diethylene glycolmaieate. triallyl phosphate and a small amount of an organic peroxide asa polymerization catalyst and 26 continuing said heating until aninsoluble. iniusible resin results.

9. The method of producing an insoluble, iniusible resinous compositionwhich comprises iorming a mixture of diethyiene glycol maleate, trlallylphosphate and a small amount of an or ganic peroxide as a polymerizationcatalyst, and heating the said mixture until an insoluble and infusibleresin results.

10 10. A polymerizabie composition comprising trialiyl phosphate and acompatible, polymerizable, unsaturated alkyd resin.

11. A process which comprises polymerizing a homogeneous mixtureincluding triallyl phosphate 16 and a compatible, polymerizable,unsaturated alkyd resin.

EDWARD L. KROPA.

Certificate of Correction Patent No. 2,409,633.

October 22, 1946.

EDWARD L. KROPA It is hereby certified that errors appear in the printedspecification of the above numbered patent requiring correction asfollows:

Column 4, line 19, for that port-ion of the formula reading CH,OCC readUH -00C; lines 35 to 38 inclusive, for

"CHr-CH CHr-GH OHS-OH column 5, line 50, after state insert a period;column 8, line 29, for alkyl read alkyd; line 34 after parts and beforethe comma, insert a closing parenthesis; line 49, for 99 3. read 90 0.;line 62, after parts first occurrence, insert a closin parenthesis;column 9, line 52, for "equare read squarei' same line, for celar reaclear; column 13,1ine 46, for to read A to co umn 23, line 41, forresins or read resins are; and that the said Letters Patent should beread with these corrections therein that the same may conform to therecord of the case in the Patent Ofiice.

Signed and sealed this 4th day of February, A. D. 1947.

LESLIE FRAZER,

First Assistant Commissioner of Patents.

25 (1) and (2) beinc oopolymerizable and compatible.

6. As a new product, a resinous interpolymer obtained byinterpolymerization of a mixture of copolymerizable materials consistingof diethylene glycol maleate and triallyi phosphate.

'7. The method of producing new synthetic compositions which comprisespolymerizing a polymerizable composition comprising (1) triallylphosphate, (2) a polymerizable unsaturated alkyd resin compatible withthe said phosphate of (l), and (3) a catalyst for accelerating thecopolymerization of the materials oi (l) and (2).

8. The method of producing an insoluble and ini'usible resinouscomposition which comprises heating a mixture of diethylene glycolmaieate. triallyl phosphate and a small amount of an organic peroxide asa polymerization catalyst and 26 continuing said heating until aninsoluble. iniusible resin results.

9. The method of producing an insoluble, iniusible resinous compositionwhich comprises iorming a mixture of diethyiene glycol maleate, trlallylphosphate and a small amount of an or ganic peroxide as a polymerizationcatalyst, and heating the said mixture until an insoluble and infusibleresin results.

10 10. A polymerizabie composition comprising trialiyl phosphate and acompatible, polymerizable, unsaturated alkyd resin.

11. A process which comprises polymerizing a homogeneous mixtureincluding triallyl phosphate 16 and a compatible, polymerizable,unsaturated alkyd resin.

EDWARD L. KROPA.

Certificate of Correction Patent No. 2,409,633.

October 22, 1946.

EDWARD L. KROPA It is hereby certified that errors appear in the printedspecification of the above numbered patent requiring correction asfollows:

Column 4, line 19, for that port-ion of the formula reading CH,OCC readUH -00C; lines 35 to 38 inclusive, for

"CHr-CH CHr-GH OHS-OH column 5, line 50, after state insert a period;column 8, line 29, for alkyl read alkyd; line 34 after parts and beforethe comma, insert a closing parenthesis; line 49, for 99 3. read 90 0.;line 62, after parts first occurrence, insert a closin parenthesis;column 9, line 52, for "equare read squarei' same line, for celar reaclear; column 13,1ine 46, for to read A to co umn 23, line 41, forresins or read resins are; and that the said Letters Patent should beread with these corrections therein that the same may conform to therecord of the case in the Patent Ofiice.

Signed and sealed this 4th day of February, A. D. 1947.

LESLIE FRAZER,

First Assistant Commissioner of Patents.

cuunemucmm EDWARD n mom It is hereby certified that error appears in theprinted spemfi ti 1' 1;]: be numbered tent requiring correction asfollows: Column 6, M303; :8 inzltmiv ot 1m. two 00 umns of table, [or

l'ltent No. 2,409,633. October 22, 1946.

read no 7 v 8 and flmtthe said Lem mm should be read with thiscorrection therein am the some may conform to the record of the case inthe Patent Oflico.

Signedandaealodthis4thdayofMarch,A.D.19-17.

LESLIE FRAZER,

Fin! Assistant flommiuionar of PM,

